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题名	新型含氟季铵盐的合成、表征及性质研究
作者	周君
学位类别	硕士
答辩日期	2010-05-25
授予单位	中国科学院研究生院
导师	张懿 ; 李会泉
关键词	季铵盐 四氟铝酸盐 合成 表征 电化学性质
其他题名	Synthesis, Characterization and properties of new fluorine-containing quaternary ammonium salt
学位专业	化学工艺
中文摘要	离子液体因具有优良的物理、化学性质，引起了人们的广泛关注，已经在许多领域中得到了广泛应用。功能化含氟离子液体的制备与应用是离子液体领域研究的热点，氟原子的引入赋予了离子液体很多有价值的特定功能。有机鎓的四氟铝酸盐作为一种新型含氟离子液体，可以用于铝电解电容器用电解液等。但目前所报道有机鎓的四氟铝酸盐的合成方法均以剧毒的氟化氢或者易爆的烷基铝化合物为原料，对设备要求高，危险性大，操作复杂，且关于其物理及电化学性质也没有详细地报道。本文采用两种方法合成了四种季铵类四氟铝酸盐，并对其物理及电化学性质进行了系统研究，旨在开发一种熔点相对较低、电导率高、热稳定性和电化学稳定性好的新型含氟离子液体，主要研究内容如下： (1) 采用两种合成路线分别制备了四种季铵类四氟铝酸盐。一是采用不同烷基取代的氟化铵三水化合物与氟化铝三水化合物反应制备了阳离子分别为四甲基铵、四乙基铵、四丙基铵及四丁基铵，阴离子为四氟铝酸根的季铵类四氟铝酸盐, 在优化的反应条件下，其收率约为90%；采用25%的四丁基氢氧化铵水溶液与六氟铝酸铵反应的新方法合成了四丁基四氟铝酸铵，在优化的反应条件下，得到了高纯度产品，收率约为56%；与文献报道的其他方法相比，该法安全性好，对设备要求低，操作简单。 (2) 使用元素分析、1H-NMR、19F-NMR、MSI-MS、FTIR、Raman等分析表征手段对四种产品的结构进行了确认，证明所得产品即为目标产物。对两种合成方法所得的四丁基四氟铝酸铵产品结构进行了对比分析，发现其结果完全一致，均为目标产物。 (3) 对四种季铵类四氟铝酸盐的物理及电化学性质进行了对比分析，发现四丙基四氟铝酸铵和四丁基四氟铝酸铵具有较宽的液程范围，是一种很有潜力的电解质。在220~300 ℃范围内，熔融态四丙基四氟铝酸铵和四丁基四氟铝酸铵的电导率随着温度的升高逐渐增加。电化学稳定性随着温度的升高逐渐降低，熔融态四丙基四氟铝酸铵的电化学窗口由220℃的4.6 V降到了280℃的4.3 V；熔融态四丁基四氟铝酸铵的电化学窗口由220℃的4.7 V降到了260℃的4.2 V。
英文摘要	Ionic liquids which have been used widely in many fields have aroused people's widespread interest owing to their good physical and chemical properties.Preparation and applications of functional fluorine-containing ionic liquids have been paid many attention. As a result of the introduction of fluorine atoms, ionic liquids get many valuable features. Organic cation salts of tetrafluoroaluminate anion as new fluorine-containing ionic liquids, can be used for electrolytes of aluminum electrolytic capacitor. However, currently reported synthesis of organic cation salts of the tetrafluoroaluminate anion are all from highly toxic hydrogen fluoride or explosive aluminium alkyls, which are corrosive, dangerous and complicated. In addition the physical and electrochemical properties of organic cation salts of the tetrafluoroaluminate anion have not been reported in detail. In this paper four kinds of quaternary ammonium cation salts of tetrafluoroaluminate anion were synthesized by two methods, and their physical and electrochemical properties were studied seriously aiming to develop new fluorine-containing ionic liquids which have relatively low melting points, high conductivities, good thermal and electrochemical stabilities. The main contents are as follows: (1) Four kinds of quaternary ammonium cation salts of tetrafluoroaluminate anion were prepared by two synthetic routes. Firstly, (CH3)4NAlF4, (C2H5)4NAlF4, (C3H7)4NAlF4 and (C4H9)4NAlF4 were prepared from (CnH2n+1)4NF·xH2O and AlF3·3H2O. Under the feasible reaction conditions, the yield of four products was about 90%. (C4H9)4NAlF4 was also synthesized from 25%(w) (C4H9)4NOH aqueous solution and (NH4)3AlF6 by our new method. Under the optimum reaction conditions, high-purity (C4H9)4NAlF4 was obtained and the yield was achieved up to 56%. Compared to other methods reported in the literature, they have good security and low requirement on the device and are easy to operate. (2) (CH3)4NAlF4, (C2H5)4NAlF4, (C3H7)4NAlF4 and (C4H9)4NAlF4 were characterized by using elemental analysis, 1H-NMR, 19F-NMR, MSI-MS, FTIR and Raman. It was confirmed that the obtained ionic liquids were what we expected. In addition, comparing the products (C4H9)4NAlF4 which were synthesized by two methods, we found that they were identical. (3) By the comparative analysis of physical and electrochemical properties of four kinds of quaternary ammonium cation salt of tetrafluoroaluminate anion, we find that (C3H7)4NAlF4 and (C4H9)4NAlF4 have a wide range of liquid state, which are potential electrolytes. With the increase of temperature, conductivities of molten (C3H7)4NAlF4 and (C4H9)4NAlF4 increase in the range of 220~300 ℃. With the increase of temperature, electrochemical stabilitiesof molten (C3H7)4NAlF4 and (C4H9)4NAlF4 decrease. The electrochemical window of molten (C3H7)4NAlF4 decline to 4.3 V at 280 ℃ compared to 4.6 V at 220 ℃, and that of molten (C4H9)4NAlF4 decrease to 4.2 V at 260 ℃ compared to 4.7 V at 220 ℃.
语种	中文
公开日期	2013-09-22
页码	72
内容类型	学位论文
源URL	[http://ir.ipe.ac.cn/handle/122111/1619]
专题	过程工程研究所_研究所（批量导入）
推荐引用方式 GB/T 7714	周君. 新型含氟季铵盐的合成、表征及性质研究[D]. 中国科学院研究生院. 2010.

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